Compositions comprising zwitterionic ester ammonioalkanoates containing a heterocyclic group

ABSTRACT

The present invention provides compositions utilizing a zwitterionic ester ammonioalkanoate surfactant according to Formula 1 and an ingredient selected from the group consisting a surfactant other than said zwitterionic ester ammonioalkanoate surfactant, emulsifiers, conditioning agents, emollients, moisturizers, humectants, thickeners, lubricants, chelating agents, fillers, binding agents, anti-oxidants, preservatives, active ingredients, fragrances, dyes, buffering agents, exfoliates, pH adjusters, inorganic salts, solvents, viscosity controlling agents and opacifying agents, wherein the composition is substantially free of alkylamidoamine and aminoalkylamine.

This application is a continuation of U.S. application Ser. No.14/518,476 filed on Oct. 20, 2014, now U.S. Pat. No. 9,381,147, issuedon Jul. 5, 2016, the complete disclosure of each of which is herebyincorporated herein by reference for all purposes.

PARTIES TO JOINT RESEARCH AGREEMENT

Inventions described or claimed herein were made pursuant to a JointResearch Agreement between Eastman Chemical Company and Johnson &Johnson Consumer & Personal Product Worldwide, a division of Johnson &Johnson Consumer Companies Inc.

FIELD OF INVENTION

The present invention relates to compositions comprising zwitterionicester ammonioalkanoate surfactants, as defined herein.

BACKGROUND OF THE INVENTION

Cleansing compositions are used to apply to the hair and/or skin ofhumans in order to provide cleansing of the respective part of the bodyto be cleaned. With respect to cleansing skin, cleansing formulationsare designed to remove dirt, sweat, sebum, and oils from the skin, wherecleansing is achieved through the use of conventional surfactants thataid in the uplifting of dirt and solubilization and removal of oilysoils from the skin. In addition to removing unwanted materials from theskin, cleansing helps to promote normal exfoliation, and therebyrejuvenates the skin. Conventional detergents, such as cationic, anionicand non-ionic surfactants, are widely used in a variety of cleansingcompositions to impart such cleansing properties.

Also, zwitterionic surfactants, like betaines, sultaines andamphoacetates, are widely used in a variety of cleansing compositions.They are best known to generate desirable viscosity, foam and mildnessin cleansing formulations, the most commonly used being cocamidopropylbetaine. Other examples include lauramidopropyl betaine, cocamidopropylhydroxyl sultaine, lauramidopropyl hydroxyl sultaine, sodiumlauroamphoacetate, sodium cocoamphoacetate, disodium cocoamphodipropionate and disodium lauroampho dipropionate, and the like.However, these zwitterionic surfactants all bear an amide-moiety andrecently have been recognized as possible allergens. In particular,cocamidopropyl betaine is now part of allergy screening tests. Further,allergens and skin irritants such as alkylamidoamines andaminoalkylamines are present in all of the zwitterionic surfactantsnoted above, the former an intermediate formed during the synthesis ofthe above zwitterionic surfactants and the latter an unreacted rawmaterial used for the synthesis.

Applicants have recognized the desirability of developing cleansers thatare substantially free of zwitterionic surfactants bearing anamide-moiety and possibly alkylamidoamines and aminoalkylamines, whilestill fulfilling the demand for desirable viscosity, foam and mildness.

Zwitterionic surfactants are best suitable to help generating desirableviscosity, foam and mildness in cleansing formulations. Accordingly,applicants have recognized the need to develop cleansing compositionscontaining zwitterionic surfactants which do not contain an amide moietyand that are substantially free of alkylamidoamines and aminoalkylamineimpurities, and that exhibit desirable viscosity, foam and mildness forconsumer use.

SUMMARY OF THE INVENTION

The present invention provides compositions comprising a zwitterionicester ammonioalkanoate surfactant according to Formula 1, hereinafterreferred to as “ZEA surfactants”, and an ingredient selected from thegroup consisting of a surfactant other than the zwitterionic esterammonioalkanoate surfactant according to Formula 1, emulsifiers,conditioning agents, emollients, moisturizers, humectants, thickeners,lubricants, chelating agents, fillers, binding agents, anti-oxidants,preservatives, active ingredients, fragrances, dyes, buffering agents,exfoliants, pH adjusters, inorganic salts, solvents, viscositycontrolling agents and opacifying agents, wherein the composition issubstantially free of alkylamidoamine and aminoalkylamine.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have discovered that compositions of the present inventionovercome the disadvantages of the prior art and provide compositionsthat exhibit desirable viscosity and/or foaming action, as compared tothe prior art, while maintaining excellent mildness to the skin andeyes. The compositions are substantially free of alkylamidoamine andaminoalkylamine impurities and substantially free of zwitterionicsurfactants bearing an amide-moiety. For example, as shown in theExamples, compositions comprising one or more ZEA surfactants tend toexhibit better viscosity building properties, similar or better foamingaction, and at least comparable mildness (measured by EpiDerm™ andEpiOcular™ Test) compared to zwitterionic surfactants bearing anamide-moiety and/or containing alkylamidoamine and/or aminoalkylamineimpurities, like cocamidopropyl betaine, cocoamphoactetate andcocamidopropyl hydroxy sultaine.

As used herein the term “zwitterionic ester ammonioalkanoatesurfactants”, or “ZEA surfactants”, refers to a zwitterionic surfactantaccording to Formula 1:

where R₁ is a linear, branched, saturated or unsaturated C5 to C21hydrophobe;R₂ is a linear, branched, or cyclic alkyl, hydroxyalkyl, or aromaticgroup;R₃ is a linear or branched alkyl, hydroxyalkyl, or aromatic group;R₄ is a linear or branched alkyl, hydroxyalkyl, or aromatic group;R₅ is a linear or branched alkyl, hydroxyalkyl, or aromatic group; andany of R₂, R₄, or R₅ can by linked in a cyclic structure; andX is —CO2-, —SO3-, or —SO4-.

One specific example of a ZEA surfactant according to Formula 1 is3-((3-(lauroyloxy)butyl)dimethylammonio)-2-hydroxypropanesulfonate,shown in Formula 2:

An example of a ZEA surfactant according to Formula 1 bearing a cyclicgroup is3-(4-lauroyloxy-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate,shown in Formula 3,

where R₂ and R₄ are linked in a cyclic structure, forming a piperidiniumgroup.

Typically, compositions of the present invention will comprise fromabout 0.1% to about 30% w/w of ZEA surfactants, or from about 0.5% toabout 15% w/w of ZEA surfactants, or from about 1% to about 10% w/w ofZEA surfactants, or from about 1.5% to about 7% w/w of ZEA surfactants,or about 1.5% to about 5% of ZEA surfactants, or about 1.5% to about3.75% of ZEA surfactants, or about 2.25% to about 3.75% of ZEAsurfactants.

As used herein the term “zwitterionic ester ammonioalkanoate sulfonatesurfactant” refers to a ZEA surfactant where X is —SO₃—.

As used herein the term “zwitterionic ester ammonioalkanoate sulfatesurfactant” refers to a ZEA surfactant where X is —SO₄—.

Preferably, ZEA surfactants are free of alkylamidoamines andaminoalkylamines. They exhibit an ester bond between R₁ and R₂, whereasthe prior art exhibits an amide moiety. Thus, they do not containamidoamines or aminoalkylamines.

All percentages listed in this specification are percentages by weight,unless otherwise specifically mentioned.

As used herein, the term “substantially free of alkylamidoamine andaminoalkylamine” means a composition that comprises alkylamidoamineand/or aminoalkylamine at maximum levels that mitigate or avoid thedetrimental allergic or skin-irritating effects caused byalkylamidoamine and/or aminoalkylamine, for example, less than 0.05% w/wof alkylamidoamine and/or aminoalkylamine. Even more preferable,compositions are free of alkylamidoamine and aminoalkylamine.

Certain embodiments of the present invention may comprise surfactantsother than ZEA surfactants. For example, compositions may furthercomprise anionic, cationic, non-ionic and/or zwitterionic surfactantsother than ZEA surfactants. In other embodiments, compositions may besubstantially free of surfactants other than ZEA surfactants. As usedherein, the term “substantially free of surfactant other than ZEAsurfactants” means a composition that comprises less than 0.5%, or lessthan 0.1%, and more preferably less than 0.05% by weight of totalsurfactant other than ZEA surfactants. Even more preferable,compositions are free of surfactants other than ZEA surfactants. When asurfactant other than the ZEA surfactant is used, the ratio of ZEAsurfactant to surfactant other than the ZEA surfactant (w/w) may be fromabout 0.003 to about 300, or about 0.1 to about 100, or about 0.1 toabout 10, or about 0.1 to about 5, or about 0.3 to about 3.

As used herein, the term “anionic surfactant” refers to a surfactantmolecule bearing a negative charge and no positive charge. Suitableanionic surfactants include those selected from the following classes ofsurfactants: alkyl sulfates, alkyl ether sulfates, alkyl monoglycerylether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkyl sulfosuccinamates,alkyl amidosulfosuccinates, alkyl carboxylates, alkylamidoethercarboxylates, alkyl succinates, fatty acyl sarcosinates, fattyacyl amino acids, fatty acyl taurates, fatty alkyl sulfoacetates, alkylphosphates, and mixtures of two or more thereof. In certain embodiments,the compositions of the present invention are substantially free ofanionic surfactants, and preferably are free of anionic surfactant.

As used herein, the term “sulfated anionic surfactant” refers to anionicsurfactants containing a —SO₄ ⁻M⁺ group, with M⁺ being absent, or H⁺ orNH₄ ⁺ or Na⁺ or K⁺ or other monovalent or multivalent anion. Examples ofsulfated anionic surfactants include, but are not limited to, sodiumlauryl sulfate and sodium laureth sulfate. In certain embodiments, thecompositions of the present invention are substantially free of sulfatedanionic surfactant, and preferably are free of sulfated anionicsurfactant.

As used herein, the term “nonionic surfactant” refers to a surfactantmolecule bearing no electrostatic charge. Any of a variety of nonionicsurfactants are suitable for use in the present invention. Examples ofsuitable nonionic surfactants include, but are not limited to, fattyalcohol acid or amide ethoxylates, monoglyceride ethoxylates, sorbitanester ethoxylates alkyl polyglycosides, mixtures thereof, and the like.Certain preferred nonionic surfactants include polyethyleneoxyderivatives of polyol esters, wherein the polyethyleneoxy derivative ofpolyol ester (1) is derived from (a) a fatty acid containing from about8 to about 22, and preferably from about 10 to about 14 carbon atoms,and (b) a polyol selected from sorbitol, sorbitan, glucose, α-methylglucoside, polyglucose having an average of about 1 to about 3 glucoseresidues per molecule, glycerine, pentaerythritol and mixtures thereof,(2) contains an average of from about 10 to about 120, and preferablyabout 20 to about 80 ethyleneoxy units; and (3) has an average of about1 to about 3 fatty acid residues per mole of polyethyleneoxy derivativeof polyol ester. Examples of such preferred polyethyleneoxy derivativesof polyol esters include, but are not limited to PEG-80 sorbitan laurateand Polysorbate 20. PEG-80 sorbitan laurate is a sorbitan monoester oflauric acid ethoxylated with an average of about 80 moles of ethyleneoxide. Polysorbate 20 is the laurate monoester of a mixture of sorbitoland sorbitol anhydrides condensed with approximately 20 moles ofethylene oxide.

Another class of suitable nonionic surfactants includes long chain alkylglucosides or polyglucosides, which are the condensation products of (a)a long chain alcohol containing from about 6 to about 22, and preferablyfrom about 8 to about 14 carbon atoms, with (b) glucose or aglucose-containing polymer. Preferred alkyl gluocosides comprise fromabout 1 to about 6 glucose residues per molecule of alkyl glucoside. Apreferred glucoside is decyl glucoside, which is the condensationproduct of decyl alcohol with a glucose oligomer

Another class of suitable nonionic surfactants includes alkanolamides,like cocamide MEA and cocamide DEA.

As used herein, “zwitterionic surfactant other than a ZEA surfactant”refers to an amphiphilic molecule comprising a hydrophobic group and oneor more hydrophilic groups comprising two moieties of opposite formalcharges, or capable of bearing opposite formal charges (as a function ofacid-base properties and solution pH). Sometimes such surfactants arealso referred to as “amphoteric surfactants”. Examples of zwitterionicsurfactants other than a ZEA surfactant include:

Alkylamidoalkyl betaines of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andx=1-4. Examples include cocamidoethyl betaine (RCO=coco acyl, x=2),cocamidopropyl betaine (RCO=coco acyl, x=3), lauramidopropyl betaine(RCO=lauroyl, and x=3), myristamidopropyl betaine (RCO=myristoyl, andx=3), soyamidopropyl betaine (R=soy acyl, x=3), and oleamidopropylbetaine (RCO=oleoyl, and x=3).

Alkylamidoalkyl hydroxysultaines of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include cocamidopropyl hydroxysultaine (RCO=coco acyl, x=3),lauramidopropyl hydroxysultaine (RCO=lauroyl, and x=3),myristamidopropyl hydroxysultaine (RCO=myristoyl, and x=3), andoleamidopropyl hydroxysultaine (RCO=oleoyl, and x=3).

Alkylamidoalkyl sultaines of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include cocamidopropyl sultaine (RCO=coco acyl, x=3),lauramidopropyl sultaine (RCO=lauroyl, and x=3), myristamidopropylsultaine (RCO=myristoyl, and x=3), soyamidopropyl betaine (RCO=soy acyl,x=3), and oleamidopropyl betaine (RCO=oleoyl, and x=3).

Amphoacetates of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include sodium lauroamphoacetate(RCO=lauroyl and M⁺=Na⁺) and sodium cocoamphoacetate (RCO=coco acyl andM⁺=Na⁺).

Amphodiacetates of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include disodium lauroamphodiacetate(RCO=lauroyl and M=Na⁺) and disodium cocoamphodiacetate (RCO=coco acyland M=Na⁺).

Amphopropionates of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include sodium lauroamphopropionate(RCO=lauroyl and M⁺=Na⁺) and sodium cocoamphopropionate (RCO=coco acyland M⁺=Na⁺).

Amphodipropionates of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include disodium lauroamphodipropionate(RCO=lauroyl and M⁺=Na⁺) and disodium cocoamphodipropionate (RCO=cocoacyl and M⁺=Na⁺).

Amphohydroxypropylsulfonates of the formula:

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as sodium lauroamphohydroxypropylsulfonate(RCO=lauroyl and M⁺=Na⁺) and sodium cocoamphohydroxypropylsulfonate(RCO=coco acyl and M⁺=Na⁺).

Other examples include amphohydroxyalkylphosphates and alkylamidoalkylamine oxides.

In certain embodiments of the present invention, the composition mayfurther comprise an inorganic salt. Inorganic salts that are suitablefor use in this invention include, but are not limited to, sodiumchloride, potassium chloride, sodium bromide, potassium bromide,ammonium chloride, ammonium bromide and other mono-valent as well asmulti-valent ion containing salts. Typically, compositions of thepresent invention will comprise from about 0.05% to about 6% w/w ofinorganic salt, or from about 0.1% to about 4% w/w of inorganic salt, orfrom about 0.1% to about 2% w/w of inorganic salt, or from about 0.1% toabout 1.5% w/w of inorganic salt.

The pH of composition of the present invention is adjusted to preferablyfrom about 3 to about 9, more preferably from about 3.5 to about 7, andmost preferably from about 4 to about 6. The pH of the composition maybe adjusted as low as 3 provided that formula stability and performance(e.g. foaming, mildness and viscosity) are not negatively affected. ThepH of the composition may be adjusted to the appropriate acidic valueusing any cosmetically acceptable organic or inorganic acid, such ascitric acid, acetic acid, glycolic acid, lactic acid, malic acid,tartaric acid, hydrochloric acid, combinations of two or more thereof orthe like.

In certain embodiments of the present invention, the composition mayfurther comprise a cationic surfactant. Classes of cationic surfactantsthat are suitable for use in this invention include, but are not limitedto, alkyl quaternaries (mono, di, or tri), benzyl quaternaries, esterquaternaries, ethoxylated quaternaries, alkyl amines, and mixturesthereof, wherein the alkyl group has from about 6 carbon atoms to about30 carbon atoms, with about 8 to about 22 carbon atoms being preferred.

In certain embodiments of the present invention, the compositioncomprises cationic conditioning polymers. Examples of suitable cationicconditioning polymers include cationic cellulose and its derivatives;cationic guar and its derivatives; and diallyldimethylammonium chloride.The cationic cellulose derivative may be a polymeric quaternary ammoniumsalt derived from the reaction of hydroxyethyl cellulose with atrimethylammonium substituted epoxide, known as Polyquaternium-10. Thecationic guar derivative may be a guar hydroxypropyltrimonium chloride.Other useful cationic conditioning polymers are those derived from themonomer diallyldimethylammonium chloride. The homopolymer of thismonomer is Polyquatemium-6. The copolymer of diallyldimethylammoniumchloride with acrylamide is known as Polyquatemium-7. Other suitableconditioning polymers include those disclosed in U.S. Pat. No.5,876,705, which is incorporated herein by reference.

The composition of this invention may further contain any otheringredients or additives typically used in personal care products, e.g.,dermatological or in cosmetic formulations, including activeingredients. Examples of further ingredients or additives aresurfactants, emulsifiers, conditioning agents, emollients, moisturizers,humectants, thickeners, lubricants, chelating agents, fillers, bindingagents, anti-oxidants, preservatives, active ingredients, fragrances,dyes, buffering agents, exfoliates, pH adjusters, solvents, viscositycontrolling agents and opacifying agents, and the like, provided thatthey are physically and chemically compatible with the other componentsof the composition. Active ingredients may include, without limitation,anti-inflammatory agents, anti-bacterials, anti-fungals, anti-itchingagents, moisturizing agents, plant extracts, vitamins, and the like.Also included are sunscreen actives which may be inorganic or organic innature. Of particular interest are any active ingredients suited fortopical application of personal care compositions.

The following examples are meant to illustrate the present invention,not to limit it thereto.

EXAMPLES

Test methods used in the Examples are described as follows:

Zero-Shear Viscosity Test:

Determinations of zero-shear apparent viscosity of the cleansingcompositions were conducted on a controlled-stress rheometer (AR-2000,TA Instruments Ltd., New Castle, Del., USA). Steady-state shear stresssweeps were performed at 25.0±0.1° C. using a cone-plate geometry. Dataacquisition and analysis were performed with the Rheology Advantagesoftware v4.1.10 (TA Instruments Ltd., New Castle, Del., USA).Zero-shear apparent viscosities for Newtonian fluids are reported as theaverage of viscosity values obtained over a range of shear stresses(0.02-1.0 Pa). For pseudoplastic (shear-thinning) fluids, zero-shearapparent viscosities were calculated via the fitting of shear stresssweep data to an Ellis viscosity model. Except otherwise stated,viscosities are given in CentiPoise (cps).

Formulation Foam Test:

The following Formulation Foam Test was performed on various cleansingcompositions to determine the foam volume upon agitation according tothe present invention. First, a solution of the test composition isprepared in simulated tap water. To represent the hardness of tap water,0.455 g of calcium chloride dihydrate (Sigma-Aldrich) is dissolved per1000 g of DI water, and mixed for 15 minutes prior to use. One (1.0) orfive (5.0) grams of test composition is weighed, and this solution isadded to 1000 g and mixed until homogeneous for 15 minutes prior to use.To determine the Formulation Foam Volume, the test composition (1000 mL)was added to the sample tank of a SITA R-2000 foam tester (commerciallyavailable from Future Digital Scientific, Co.; Bethpage, N.Y.). The testparameters were set to repeat three runs (series count=3) of 250 mlsample size (fill volume=250 ml) with thirteen stir cycles (stircount=13) for a 15 second stir time per cycle (stir time=15 seconds)with the rotor spinning at 1200 RPM (revolution=1200) at a temperaturesetting of 30° C.±2° C. Foam volume data was collected at the end ofeach stir cycle and the average and standard deviation of the three runswas determined. The Maximum Foam Volume was reported for each Example asthe value after the thirteenth stir cycle.

EpiDerm™ Test:

Upon receipt of the EpiDerm™ Skin Kit (MatTek Corporation), thesolutions were stored as indicated by the manufacturer. The EpiDerm™tissues were stored at 2-8° C. until use. On the day of dosing, EpiDerm™Assay Medium was warmed to approximately 37° C. Nine-tenths mL of AssayMedium were aliquotted into the appropriate wells of 6-well plates. The6-well plates were labeled to indicate test article and exposure time.Each EpiDerm™ tissue was inspected for air bubbles between the agarosegel and cell culture insert prior to opening the sealed package. Tissueswith air bubbles covering greater than 50% of the cell culture insertarea were not used. The 24-well shipping containers were removed fromthe plastic bag and their surfaces were disinfected with 70% ethanol.

The EpiDerm™ tissues were transferred aseptically into the 6-wellplates. The EpiDerm™ tissues were then incubated at 37±1° C. in ahumidified atmosphere of 5±1% CO2 in air (standard culture conditions)for at least one hour. The medium was aspirated and 0.9 mL of freshAssay Medium were added to each assay well below the EpiDerm™ tissues.The plates were returned to the incubator until treatment was initiated.Upon opening the bag, any remaining unused tissues were briefly gassedwith an atmosphere of 5% CO2/95% air and placed back at 2-8° C. forlater use. The test articles were administered to the test system as 10%w/v dilutions in sterile, deionized water. Each test article dilutionwas prepared by weighing approximately 1,000 mg of the test article intoa pre-labeled conical tube. Sterile, deionized water was added until a10% w/v dilution was achieved and the tube was vortexed forapproximately 1 minute prior to application. In the following, each testarticle dilution is referred to as the test article.

The test articles were tested in duplicate EpiDerm™ tissues at fourexposure times of 4, 8, 16, and 24 hours. One hundred microliters ofeach test article were applied to each EpiDerm™ tissue. The negativecontrol, 100 μL of sterile, deionized water, was treated in duplicatetissues for 1, 4, 16, and 24 hours. The positive control, 100 μL of 1%Triton®-X-100 (Fisher), was treated in duplicate tissues for 4 and 8hours. The treated tissues were then incubated at standard cultureconditions for the appropriate exposure time. Two sets of dilutions wereprepared for the study: one set for the 4, 8, and 24 hours treatment andone set for the 16 hours treatment. A 1.0 mg/mL solution of MTT in warmMTT Addition Medium was prepared no more than 2 hours before use. Afterthe appropriate exposure time, the EpiDerm™ tissues were extensivelyrinsed with Calcium and Magnesium-Free Dulbecco's Phosphate BufferedSaline (Ca²⁺Mg²⁺-Free DPBS) and the wash medium was decanted.Three-tenths mL of MTT reagent were added to designated wells in aprelabeled 24-well plate. The EpiDerm™ tissues were transferred to theappropriate wells after rinsing. The plates were incubated forapproximately three hours at standard culture conditions. After theincubation period with MTT solution, the EpiDerm™ tissues were blottedon absorbent paper, cleared of excess liquid, and transferred to aprelabeled 24-well plate containing 2.0 mL of isopropanol in eachdesignated well. The plates were covered with parafilm and stored in therefrigerator (2-8° C.) until the last exposure time was harvested. Thenthe plates were shaken for at least two hours at room temperature. Atthe end of the extraction period, the liquid within the cell cultureinserts was decanted into the well from which the cell culture insertwas taken. The extract solution was mixed and 200 μL were transferred tothe appropriate wells of a 96-well plate. Two hundred of isopropanolwere placed in the two wells designated as the blanks. The absorbance at550 nm (OD₅₅₀) of each well was measured with a Molecular Devices' Vmaxplate reader.

The raw absorbance values were captured. The mean OD₅₅₀ value of theblank wells was calculated. The corrected mean OD₅₅₀ value of thenegative control(s) was determined by subtracting the mean OD₅₅₀ valueof the blank wells from their mean OD₅₅₀ values. The corrected OD₅₅₀value of the individual test article exposure times and the positivecontrol exposure times was determined by subtracting the mean OD₅₅₀value of the blank wells from their OD₅₅₀ values.

Corr. test article exposure time OD₅₅₀=Test article exposure timeOD₅₅₀−Blank mean OD₅₅₀ The following percent of control calculationswere made:

${\%\mspace{14mu}{Viability}} = {\frac{{Final}\mspace{14mu}{corrected}\mspace{14mu}{OD}_{550}\mspace{14mu}{of}\mspace{14mu}{Test}\mspace{14mu}{Article}\mspace{14mu}{or}\mspace{14mu}{Positive}\mspace{14mu}{Control}}{{corrected}\mspace{14mu}{mean}\mspace{14mu}{OD}_{550}\mspace{14mu}{of}\mspace{14mu}{Negative}\mspace{14mu}{Control}} \times 100}$The individual % of control values were then averaged to calculate themean % of control per exposure time. Test article and positive controlviability calculations were performed by comparing the corrected OD₅₅₀values of each test article or positive control exposure time to arelevant negative control.

Exposure time response curves were plotted with the % of Control on theordinate and the test article or positive control exposure time on theabscissa. The ET₅₀ value was interpolated from each plot. To determinethe ET₅₀, the two consecutive points were selected, where one exposuretime resulted in a relative survival greater than 50%, and one exposuretime resulted in less than 50% survival. The two select exposures wereused to determine the slope and the y-intercept for the equationy=m(x)+b. Finally, to determine the ET₅₀, the equation was solved fory=50. If all of the exposure times showed greater than 50% survival, theET₅₀ value was presented as greater than the maximum exposure time.

EpiOcular™ Test:

Upon receipt of the EpiOcular™ Human Cell Construct Kit (MatTekCorporation), the solutions were stored as indicated by themanufacturer. The EpiOcular™ human cell constructs were stored at 2-8°C. until used. On the day of dosing, EpiOcular™ Assay Medium was warmedto approximately 37° C. Nine-tenths mL of Assay Medium were aliquotedinto the appropriate wells of 6-well plates. The six-well plates werelabeled to indicate test article and exposure time. The constructs wereinspected for air bubbles between the agarose gel and cell cultureinsert prior to opening the sealed package. Cultures with air bubblescovering greater than 50% of the cell culture area were not used. The24-well shipping containers were removed from the plastic bag and theirsurfaces were disinfected with 70% ethanol. The EpiOcular™ human cellconstructs were transferred aseptically into the 6-well plates. Theconstructs were then incubated at 37±1° C. in a humidified atmosphere of5±1% CO2 in air (standard culture conditions) for at least one hour. Themedium was then aspirated and 0.9 mL of fresh Assay Medium were added toeach assay well below the EpiOcular™ human cell construct. The plateswere returned to the incubator until treatment was initiated.

The test articles were administered to the test system as 3% w/vdilutions in sterile, deionized water (positive and negative control,1.0% Triton®-X-100 and Johnson's Baby Shampoo, respectively, wereadministered to the test system as 10% w/v dilutions in sterile,deionized water). Each test article dilution was prepared by weighingthe test article into a prelabeled conical tube. Sterile, deionizedwater was added until a 3% w/v or 10% w/v dilution was achieved and thetube was vortexed prior to application. For the remainder of thisreport, each test article dilution is referred to as the test article.

The EpiOcular™ cultures were treated in duplicate with the test articlesat specific exposure times (from 0.33 up to 16 hours, four time pointseach). One hundred microliters of each test article were applied to eachEpiOcular™ human cell construct. Duplicate cultures of the negativecontrol (exposure time control), 100 μL of sterile, deionized water(Quality Biological), were exposed for 0.25, 4, 8, and 24 hours.Duplicate cultures of the positive control, 100 of 0.3% Triton®-X-100(Fisher), were exposed for 15 and 45 minutes. The exposed cultures werethen incubated for the appropriate amount of time at standard cultureconditions. After the appropriate exposure time, the EpiOcular™ cultureswere extensively rinsed with Calcium and Magnesium-Free Dulbecco'sPhosphate Buffered Saline (Ca++Mg++Free-DPBS) and the wash medium wasdecanted. After rinsing, the tissue was transferred to 5 mL of AssayMedium for a 10 to 20 minute soak at room temperature to remove any testarticle absorbed into the tissue. A 1.0 mg/mL solution of MTT in warmMTT Addition Medium was prepared no more than 2 hours before use.Three-tenths mL of MTT solution were added to designated wells in aprelabeled 24-well plate. The EpiOcular™ constructs were transferred tothe appropriate wells after rinsing with Ca++Mg++Free-DPBS. The trayswere incubated for approximately three hours at standard cultureconditions. After the incubation period with MTT solution, theEpiOcular™ cultures were blotted on absorbent paper, cleared of excessliquid, and transferred to a prelabeled 24-well plate containing 2.0 mLof isopropanol in each designated well. The plates were sealed withparafilm and stored in the refrigerator (2-8° C.) until the lastexposure time was harvested. The plates were then shaken for at leasttwo hours at room temperature. At the end of the extraction period, theliquid within the cell culture inserts was decanted into the well fromwhich the cell culture insert was taken. The extract solution was mixedand 200 μL were transferred to the appropriate wells of a 96-well plate.Two hundred microliters of isopropanol were added to the two wellsdesignated as the blanks. The absorbance at 550 nm (OD₅₅₀) of each wellwas measured with a Molecular Devices Vmax plate reader.

The raw absorbance values were captured. The mean OD₅₅₀ value of theblank wells was calculated. The corrected mean OD₅₅₀ values of thenegative controls were determined by subtracting the mean OD₅₅₀ value ofthe blank wells from their mean OD₅₅₀ values. The corrected OD₅₅₀ valuesof the individual test article exposure times and the positive controlexposure times were determined by subtracting the mean OD₅₅₀ value ofthe blank wells from their OD₅₅₀ values. All calculations were performedusing an Excel spreadsheet. The following percent of controlcalculations were made:

${\%\mspace{14mu}{of}\mspace{14mu}{Control}} = {\frac{\begin{matrix}{{corrected}\mspace{14mu}{OD}_{550}\mspace{14mu}{of}\mspace{14mu}{Test}\mspace{14mu}{Article}} \\{{or}\mspace{14mu}{Positive}\mspace{14mu}{Control}\mspace{14mu}{Exposure}\mspace{14mu}{Time}}\end{matrix}\mspace{14mu}}{{appropriate}\mspace{14mu}{corrected}\mspace{14mu}{mean}\mspace{14mu}{OD}_{550}\mspace{14mu}{Negative}\mspace{14mu}{Control}} \times 100}$

Exposure time response curves were plotted with the % of Control on theordinate and the test article or positive control exposure time on theabscissa. The ET₅₀ value was interpolated from each plot. To determinethe ET₅₀, two consecutive points were selected, where one exposure timeresulted in a relative survival greater than 50%, and one exposure timeresulted in less than 50% survival. Two select points were used todetermine the slope and the y-intercept for the equation y=m(x)+b.Finally, to determine the ET₅₀, the equation was solved for y=50. Whenall of the exposure time points showed greater than 50% survival, theET₅₀ value was presented as greater than the longest test articleexposure time

ZEA Surfactants (E1-E4) Used in Inventive Compositions and ZwitterionicSurfactants Other than ZEA Surfactants (C1-C4) Used in ComparativeCompositions:

Cocamidopropyl betaine, Comparative Examples 1 and 4, were obtained fromEvonic Inc. as Tego betaine L7V and Tego betaine F-50, respectively.Sodium lauroamphoacetate, Comparative Example 2, was obtained fromSolvay Inc. as Miranol HMD. Cocamidopropyl hydroxyl sultaine,Comparative Example 3, was obtained from Solvay Inc. as Mirataine CBS.

Table 1 lists the zwitterionic ester ammonioalkanoate surfactantsaccording to Formula 1 used for Inventive Example Compositions andzwitterionic surfactants used in Comparative Compositions.

TABLE 1 Trade Activity INCI or Chemical Name Name (%)* E1 3-((3- N/A28.1* (lauroyloxy)propyl)dimethylammonio)-2- hydroxypropanesulfonate E23-(4-lauroyloxy-1-methylpiperidinium-1- N/A   88.6 **yl)-2-hydroxypropanesulfonate E3 3-lauroyloxymethyl-1-methyl- N/A 24.4*piperidinium-1-yl acetate E4 3-((3-(lauroyloxy)butyl)dimethyl- N/A 29.7*ammonio)-2-hydroxypropanesulfonate C1 Cocamidopropyl betaine Tego ®30*   betaine L7V C2 Sodium Lauroamphoacetate Miranol ® 27.5* HMD C3Cocamidopropyl hydroxyl sultaine Mirataine ® 42*   CBS C4 Cocamidopropylbetaine Tego ® 38*   betaine F50 *Activity in water. The aqueous phasemay also contain some amounts of sodium chloride and impurities, such aslauric acid. ** E2 was used as a solid also containing sodium chlorideand lauric acid.The ZEA surfactants, E1-E4, noted in Table 1, were prepared as follows:The schematic process comprises:

(a) contacting an acid or ester or a mixture of acids or esters ofFormula 4 with a dialkylamino-alcohol of Formula 5:

in the presence of an enzyme at conditions effective to form anintermediate of Formula 6:

wherein R₁, R₂, R₄, and R₅ are as defined above in Formula 1 and R₇ ishydrogen or C₁-C₆ alkyl; and

(b) contacting the intermediate of Formula 6 with a alkylating agent atconditions effective to form the ZEA surfactant of Formula 1. Suitablealkylating agents are, for example, 2-chloro acetic acid or2-hydroxy-3-chloro-propansulfonate.

As a specific example, the preparation of3-(lauryloxybutyldimethylammonio)-2-hydroxypropanesulfonate isdescribed:

Step a) Intermediate: 3-dimethylaminopropyl laurate

To a 50-mL conical bottom plastic vial was added methyl laurate (38.5mmol), dimethylaminobutanol (46.2 mmol, 1.2 eq), and Novozym 435 (400mg). A syringe was inserted through the cap and two additional holeswere punched for gas to exit. Nitrogen was bubbled at a rate sufficientto mix the contents. The vial was placed in a heating block set to 65°C. The reaction was monitored by GC/MS to observe the disappearance ofstarting material. The reaction was complete after approximately 24hours. The reaction mixture was allowed to cool. The Novozym 435 wasremoved by filtration to afford the product as a pale, yellow oil (9.2g; 67% yield) without further purification.

Step b) Final Product:3-(lauryloxypropyldimethylammonio)-2-hydroxypropanesulfonate

To a 250-mL round bottom flask with a magnetic stir bar and a condenserwas added 3-dimethylaminobutyllaurate (33.5 mmol), sodium2-hydroxy-3-chloropropanesulfonate (about 90 wt %; 35.2 mmol, 1.05equivalents), sodium carbonate (3.35 mmol; 0.10 equivalents),isopropanol (10 mL), and water (10 mL). The reaction mixture was heatedin a 90° C. oil bath for 18 hours to afford 99.5 area % conversionaccording to HPLC analysis. The mixture was concentrated at reducedpressure to 28.31 g. Water (23 g) was added and the mixture was heatedto afford solution. The mixture was placed in a 65° C. oil bath, and theheadspace was purged with nitrogen (1500 mL/min) for 2 hours to removeresidual isopropanol to a weight of 33.78 g. Water (17.5 g) was addedand the mixture was stirred at 65° C. for 10 min to afford a homogeneoussolution. The total weight of the solution was 52 g, indicating a 30%w/w solution of3-(lauryloxybutyldimethylammonio)-2-hydroxypropanesulfonate in water. ¹HNMR analysis was consistent with the product structure.

The following compositions, Inventive Examples (E5-E66) and ComparativeExamples (C5-C50) were prepared utilizing different types of formulationingredients (i.e. raw materials from various suppliers) in addition tothe ZEA surfactants. These materials, along with INCI names, trade namesand suppliers are listed below: Anionic surfactants:

-   -   Sodium laureth-2 sulfate was obtained from Solvay Inc. as        Rhodapex® ES-2K.    -   Ammonium lauryl sulfate was obtained from BASF as Standapol A.    -   Alpha olefin sulfonate was obtained from Stepan as Bioterge® AS        40-CP.    -   Sodium cocoyl glutamate was obtained from BASF as Plantapon® ACG        H2    -   Sodium starch sulfosuccinate was obtained from Akzo Nobel        Personal Care as Structure PS-111.        Non-Ionic Surfactants:    -   PEG-80 Sorbitan Laurate was obtained from Croda Inc. as Atlas        G-4280.    -   PEG-150 Distearate was obtained from Ethox Chemical as Ethox        PEG-6000 DS Special.    -   Polyglycerol-10 laurate and polyglycerol-10 oleate were obtained        from Lonza as Polyaldo® 10-1-L and Polyaldo® 10-1-O,        respectively.        Cationic (Quaternary) Conditioning Polymers:    -   Polyquaternium-10 was obtained from Dow Chemical as Ucare®        JR-400    -   Guar hydroxypropyl trimonium chloride was obtained from Solvay        Inc. as Jaguar® C17.        Humectants:    -   Glycerin was obtained from Emery Oleochemicals as Emery 917.        Chelating Agents:    -   Tetrasodium EDTA was obtained from Dow Chemical as Versene™ 100        XL.        Organic Acids/Preservatives:    -   Sodium Benzoate, NF, FCC was obtained from Emerald Performance        Materials    -   Citric acid was obtained from Formosa Laboratories Inc (for DSM)        (Taiwan).        Preservatives:    -   Phenoxy ethanol and ethylhexylglycerin were obtained from        Schülke Inc. as Euxyl® PE 9010.

Inventive Examples E5-E18 and Comparative Examples C5-C14 Preparationand Measurement of Certain Compositions of the Invention with SLES asthe Anionic Surfactant and Comparative Compositions

Compositions E5-E18 and Comparative Compositions C5-C14 were made inaccord with the following procedure: Unless otherwise indicated, allmaterials were added in amounts such that the compositions containresulting weight percent amounts of active as indicated for eachcomposition in Tables 2, 3 and 4. For example, 3.75% w/w active ofcocamidopropyl betaine (as given in table 2, C5) corresponds to 12.5%w/w Tego betaine L7V, which has an activity of 30% w/w; 3.75% w/w/30%w/w=12.5% w/w.

Preparation of Stock Solutions: Compositions E5-E18 and ComparativeCompositions C5-C14 were made using stock solutions, which had beenprepared as follows: a) Stock with zwitterionic surfactant: To anappropriately sized vessel equipped with a hotplate and overheadmechanical stirrer, the required amount of DI water (Millipore, ModelDirect Q), zwitterionic surfactant, and sodium chloride was added andmixed at 200-350 rpm until the mixture was homogeneous, for C1, E1 andE4 at room temperature, and for E2 at 50° C., respectively. Then, sodiumbenzoate and citric acid (20% w/w solution in DI water) were added atroom temperature to adjust to the desired pH value 4.4-4.6. Water wasadded in q.s. to 100 wt %, and the batch was allowed to mix untiluniform before being discharged to an appropriate storage vessel; b)Stock with anionic surfactant: To an appropriately sized vessel equippedwith a hotplate and overhead mechanical stirrer, the required amount ofDI water (Millipore, Model Direct Q), anionic surfactant, and citricacid were added and mixed at 200-350 rpm at room temperature until themixture is homogeneous. An amount of citric acid (as 20% w/w solution inDI water) was added to adjust to the desired pH value 4.4-4.6. Water wasadded in q.s. to 100% w/w and the batch was allowed to mix until uniformbefore being discharged to an appropriate storage vessel.

Compositions E5-E18 and Comparative Compositions C5-C14 were made asfollows: To an appropriately sized vessel equipped with a hotplate andoverhead mechanical stirrer, the required amount of a) stock withzwitterionic surfactant and b) stock with anionic surfactant were added.Water was added in q.s. to 100% w/w. The batch was heated to 50° C.under mixing and mixed at 200-350 rpm for 20 minutes. The batch wasallowed to cool to room temperature without mixing.

Tables 2-4 list Inventive Compositions (E5-E18) and ComparativeComposition (C5-C14) made from the inventive ZEA surfactants (E1-E4) andcomparative zwitterionic surfactants (C and C2).

The Zero Shear Viscosity were measured in accord with the Zero ShearViscosity Test as described herein. The results are shown in Table 5. Asa result, applicants discovered that zwitterionic ester ammonioalkanoatesurfactants according to Formula 1 have the tendency to build higherviscosity in comparison to zwitterionic alkylamidoamine betainesurfactants in compositions containing sodium laureth sulfate as theanionic surfactant.

TABLE 2 E5 E6 E7 E8 E9 E10 C5 C6 Activity wt. wt. wt. wt. wt. wt. wt.wt. Material Trade Name (%) % % % % % % % % Weight ratiozwitterionic/amphoteric to 1.63 1.63 1.63 1.63 1.63 1.63 1.63 1.63anionic surfactant (active to active) Zwitterionic (weight % active) E1N/A 28.1 3.75 3.75 E2 N/A 88.6 3.75 3.75 E4 N/A 29.7 3.75 3.75 C1 Tegobetaine 30 3.75 3.75 L7V Anionic (weight % active) Sodium Rhodapex ES-2K26 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 laureth-2 Sulfate Organic acidsSodium Sodium 100 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 BenzoateBenzoate, NF, FCC Citric Citric Acid 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. Acid solution to to to to to to to to pH pH pH pH pH pH pH pH4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium Chloride, 100 0 1.250 1.25 0 1.25 0 1.25 Chloride USP Water Purified water, 100 Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. USP to to to to to to to to 100% 100% 100%100% 100% 100% 100% 100%

TABLE 3 Trade Activity E11 E12 E13 E14 C7 C8 C9 C10 Material Name (%)wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % Weight ratio 0.87 0.710.51 0.36 0.87 0.71 0.51 0.36 zwitterionic/amphoteric to anionicsurfactant (active to active) Zwitterionic (weight % active) E4 N/A 29.73.75 3.75 3.75 3.75 C1 Tego 30 3.75 3.75 3.75 3.75 betaine L7V Anionic(weight % active) Sodium Rhodapex 26 4.3 5.3 7.3 10.3 4.3 5.3 7.3 10.3laureth- ES-2K 2 Sulfate Organic acids Sodium Sodium 100 0.50 0.50 0.500.50 0.50 0.50 0.50 0.50 Benzoate Benzoate, NF, FCC Citric Citric 20Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Acid Acid to to to to to to toto solution pH pH pH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5Other Sodium Sodium 100 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 ChlorideChloride, USP Water Purified 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.water, to to to to to to to to USP 100% 100% 100% 100% 100% 100% 100%100%

TABLE 4 Activity E15 E16 E17 E18 C11 C12 C13 C14 Material Trade Name (%)wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % Weight ratio 0.87 0.870.87 0.87 0.87 0.87 0.87 0.87 zwitterionic/amphoteric to anionicsurfactant (active to active) Zwitterionic (weight % active) E2 N/A 88.63.75 3.75 E4 N/A 29.7 3.75 3.75 C1 Tego betaine 30 3.75 3.75 L7V C2Miranol 27.5 3.75 3.75 HMD Anionic (weight % active) Sodium Rhodapex 264.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 laureth-2 ES-2K Sulfate Organic acidsSodium Sodium 100 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 BenzoateBenzoate, NF, FCC Citric Citric Acid 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. Acid solution to to to to to to to to pH pH pH pH pH pH pH pH4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium 100 0 0.75 0 0.75 00.75 0 0.75 Chloride Chloride, USP Water Purified 100 Q.S. Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. water, USP to to to to to to to to 100% 100%100% 100% 100% 100% 100% 100%

TABLE 5 Example Composition Information Viscosity (Cps) E5 3.75%w/w/zwitterionic surfactant NA E7 2.3% w/w/anionic surfactant (SLES)1920 E9 0% w/w sodium chloride 67210 C5 1510 E6 3.75% w/w/zwitterionicsurfactant NA E8 2.3% w/w/anionic surfactant (SLES) NA E10 1.25% w/wsodium chloride 552 C6 15600 E11 3.75% w/w/zwitterionic surfactant 37620C7 4.3% w/w/anionic surfactant (SLES) 6708 0.75% w/w sodium chloride E123.75% w/w/zwitterionic surfactant 116700 C8 5.3% w/w/anionic surfactant(SLES) 6501 0.75% w/w sodium chloride E13 3.75% w/w/zwitterionicsurfactant 134100 C9 7.3% w/w/anionic surfactant (SLES) 1384 0.75% w/wsodium chloride E14 3.75% w/w/zwitterionic surfactant 93650 C10 10.3%w/w/anionic surfactant (SLES) 2426 0.75% w/w sodium chloride E15 3.75%w/w/zwitterionic surfactant 38580 E16 4.3% w/w/anionic surfactant (SLES)35120 C11 0% w/w sodium chloride 234 C12 212 E17 3.75% w/w/zwitterionicsurfactant 2568 E18 4.3% w/w/anionic surfactant (SLES) 37620 C13 0.75%w/w sodium chloride 6708 C14 355

Inventive Examples E19-E24 and Comparative Examples C15-C16 Preparationand Measurement of Certain Compositions of the Invention with ALS as theAnionic Surfactant and Comparative Compositions

Inventive Compositions E19-E24 and Comparative Compositions C15-C16 weremade in accord with the procedure described for Compositions E5-E18 andComparative Compositions C5-C14, except that Standapol A was used as theanionic surfactant instead of Rhodapex ES-2K. Table 6 lists suchcompositions.

The Zero Shear Viscosity were measured in accord with the Zero ShearViscosity Test as described herein. The results are shown in Table 7. Asa result, applicants discovered that zwitterionic ester ammonioalkanoatesurfactants have the tendency to build equivalent or higher viscosity incomparison to zwitterionic alkylamidoamine betaine surfactants incompositions containing ammonium lauryl sulfate as the anionicsurfactant, especially at salt concentrations from 0% w/w to around 1%w/w added sodium chloride.

TABLE 6 Activity E19 E20 E21 E22 E23 E24 C15 C16 Material Trade Name (%)wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % Weight ratiozwitterionic/amphoteric 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 toanionic surfactant (active to active) Zwitterionic (weight % active) E1N/A 28.1 2.25 2.25 E2 N/A 88.6 2.25 2.25 E4 N/A 29.7 2.25 2.25 C1 Tego30 2.25 2.25 betaine L7V Anionic (weight % active) Ammonium Standapol A28 7 10 7 10 7 10 7 10 lauryl Sulfate Organic acids Sodium Sodium 1000.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Benzoate Benzoate, NF, FCCCitric Acid Citric Acid 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.solution to to to to to to to to pH pH pH pH pH pH pH pH 4.5 4.5 4.5 4.54.5 4.5 4.5 4.5 Other Sodium Sodium 100 0 1.25 0 1.25 0 1.25 0 1.25Chloride Chloride, USP Water Purified 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. water, USP to to to to to to to to 100% 100% 100% 100% 100%100% 100% 100%

TABLE 7 Example Composition Information Viscosity (Cps) E19 2.25%w/w/zwitterionic surfactant 3183 E21 7% w/w/anionic surfactant (ALS)18890 E23 0% w/w sodium chloride 83880 C15 118 E20 2.25%w/w/zwitterionic surfactant 2585 E22 10% w/w/anionic surfactant (ALS)20300 E24 1.25% w/w sodium chloride 909 C16 18920

Inventive Examples E25-E30 and Comparative Examples C17-C22 Preparationand Measurement of Certain Compositions of the Invention with AOS as theAnionic Surfactant and Comparative Compositions

Compositions E25-E30 and Comparative Compositions C17-C22 were made inaccord with the procedure described for Compositions E5-E18 andComparative Compositions C5-C14, except that Bioterge-AS 40-CP was usedas the anionic surfactant instead of Rhodapex ES-2K. Table 8 and 9 listsuch compositions.

The Zero Shear Viscosity was measured in accord with the Zero ShearViscosity Test as described herein. The results are shown in Table 10.As a result and surprisingly, applicants discovered that zwitterionicester ammonioalkanoate surfactants can build viscosity in compositionscontaining alpha olefin sulfonate as the anionic surfactant, whereaszwitterionic alkylamidoamine betaine surfactants cannot.

TABLE 8 Activity E25 E26 E27 C17 C18 C19 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to1.67 1 0.51 1.67 1 0.51 anionic surfactant (active to active)Zwitterionic (weight % active) E4 N/A 29.7 3.75 3.75 3.75 C1 Tegobetaine L7V 30 3.75 3.75 3.75 Anionic (weight % active) AlphaBioterge-AS 40-CP 39 2.25 3.75 7.35 2.25 3.75 7.35 olefin sulfonateOrganic acids Sodium Sodium Benzoate, 100 0.50 0.50 0.50 0.50 0.50 0.50Benzoate NF, FCC Citric Acid Citric Acid solution 20 Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. to to to to to to pH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5Other Sodium Sodium Chloride, 100 0.75 0.75 0.75 0.75 0.75 0.75 ChlorideUSP Water Purified water, USP 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to toto to to 100% 100% 100% 100% 100% 100%

TABLE 9 Activity E28 E29 E30 C20 C21 C22 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to 11 1 1 1 1 anionic surfactant (active to active) Zwitterionic (weight %active) E2 N/A 88.6 3.75 3.75 3.75 C1 Tego betaine L7V 30 3.75 3.75 3.75Anionic (weight % active) Alpha Bioterge-AS 40-CP 39 3.75 3.75 3.75 3.753.75 3.75 olefin sulfonate Organic acids Sodium Sodium Benzoate, 1000.50 0.50 0.50 0.50 0.50 0.50 Benzoate NF, FCC Citric Acid Citric Acidsolution 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to to to to to pH pH pH pHpH pH 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium Chloride, 100 0 0.751.25 0 0.75 1.25 Chloride USP Water Purified water, USP 100 Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. to to to to to to 100% 100% 100% 100% 100% 100%

TABLE 10 Example Composition Information Viscosity (Cps) E25 3.75%w/w/zwitterionic surfactant 1656 C17 2.25% w/w/anionic surfactant (AOS)<100 0.75% w/w sodium chloride E26 3.75% w/w/zwitterionic surfactant23410 C18 3.75% w/w/anionic surfactant (AOS) <100 0.75% w/w sodiumchloride E27 3.75% w/w/zwitterionic surfactant 35320 C19 7.35%w/w/anionic surfactant (AOS) <100 0.75% w/w sodium chloride E28 3.75%w/w/zwitterionic surfactant 225800 C20 3.75% w/w/anionic surfactant(AOS) <100 0% w/w sodium chloride E29 3.75% w/w/zwitterionic surfactant3159 C21 3.75% w/w/anionic surfactant (AOS) <100 0.75% w/w sodiumchloride E30 3.75% w/w/zwitterionic surfactant 487 C22 3.75% w/w/anionicsurfactant (AOS) <100 1.25% w/w sodium chloride

Inventive Examples E31-E36 and Comparative Examples C23-C28 Preparationand Measurement of Certain Compositions of the Invention with SCG as theAnionic Surfactant and Comparative Compositions

Compositions E31-E36 and Comparative Compositions C23-C28 were made inaccord with the procedure described for Compositions E5-E18 andComparative Compositions C5-C14, except that Plantapon ACG H2 was usedas the anionic surfactant instead of Rhodapex ES-2K and while preparingthe stock solution with the anionic surfactant, Plantapon ACG H2, thebatch was heated to 45° C. and kept at 45° C. until the stock solutionwas added to the Compositions E31-E36 and Comparative CompositionsC23-C28, as shown in Tables 11 and 12.

The Zero Shear Viscosity was measured in accord with the Zero ShearViscosity Test as described herein. The results are shown in Table 13.As a result, applicants discovered that zwitterionic esterammonioalkanoate surfactants are compatible with sodium cocoyl glutamateand have the tendency to build desired viscosity in such compositions,whereas zwitterionic alkylamidoamine betaine surfactants are notcompatible, i.e. precipitation and phase separation occur when combinedwith sodium cocoyl glutamate at a pH of around 4.5.

TABLE 11 Activity E31 E32 E33 C23 C24 C25 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to1.67 0.79 0.51 1.67 0.79 0.51 anionic surfactant (active to active)Zwitterionic (weight % active) E4 N/A 29.7 3.75 3.75 3.75 C1 Tegobetaine L7V 30 3.75 3.75 3.75 Anionic (weight % active) Sodium PlantaponACG H2 42.7 2.25 4.75 7.35 2.25 4.75 7.35 Cocoyl Glutamate Organic acidsSodium Sodium Benzoate, 100 0.50 0.50 0.50 0.50 0.50 0.50 Benzoate NF,FCC Citric Acid Citric Acid solution 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. toto to to to to pH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5 Other SodiumSodium Chloride, 100 1.25 1.25 1.25 1.25 1.25 1.25 Chloride USP WaterPurified water, USP 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to to to to to100% 100% 100% 100% 100% 100%

TABLE 12 Activity E34 E35 E36 C26 C27 C28 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to 11 1 1 1 1 anionic surfactant (active to active) Zwitterionic (weight %active) E2 N/A 88.6 3.75 3.75 3.75 C1 Tego betaine L7V 30 3.75 3.75 3.75Anionic (weight % active) Sodium Plantapon ACG H2 42.7 3.75 3.75 3.753.75 3.75 3.75 Cocoyl Glutamate Organic acids Sodium Sodium Benzoate,100 0.50 0.50 0.50 0.50 0.50 0.50 Benzoate NF, FCC Citric Acid CitricAcid solution 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to to to to to pH pHpH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium Chloride, 100 00.75 1.25 0 0.75 1.25 Chloride USP Water Purified water, USP 100 Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. to to to to to to 100% 100% 100% 100% 100% 100%

TABLE 13 Example Composition Information Viscosity (Cps) E31 3.75%w/w/zwitterionic surfactant  515 C23 2.25% w/w/anionic surfactant (SCG)NA 1.25% w/w sodium chloride E32 3.75% w/w/zwitterionic surfactant 1990C24 4.75% w/w/anionic surfactant (SCG) NA 1.25% w/w sodium chloride E333.75% w/w/zwitterionic surfactant 2360 C25 7.35% w/w/anionic surfactant(SCG) NA 1.25% w/w sodium chloride E34 3.75% w/w/zwitterionic surfactant4575 C26 3.75% w/w/anionic surfactant (SCG) NA 0% w/w sodium chlorideE35 3.75% w/w/zwitterionic surfactant 4743 C27 3.75% w/w/anionicsurfactant (SCG) NA 0.75% w/w sodium chloride E36 3.75% w/w/zwitterionicsurfactant 4000 C28 3.75% w/w/anionic surfactant (SCG) NA 1.25% w/wsodium chloride

Inventive Examples E37-E42 and Comparative Examples C29-C34 Preparationand Measurement of Certain Compositions of the Invention with SM2S asthe Anionic Surfactant and Comparative Compositions

Compositions E37-E42 and Comparative Compositions C29-C34 were made inaccord with the procedure described for Compositions E5-E18 andComparative Compositions C5-C14, except that Alphastep PC-48 was used asthe anionic surfactant instead of Rhodapex ES-2K, as shown in Tables 14and 15.

The Zero Shear Viscosity was measured in accord with the Zero ShearViscosity Test as described herein. The results are shown in Table 16.As a result and surprisingly, applicants discovered that zwitterionicester ammonioalkanoate surfactants can build viscosity in compositionscontaining SM2S as the anionic surfactant, whereas zwitterionicalkylamidoamine betaine surfactants cannot.

TABLE 14 Activity E37 E38 E39 C29 C30 C31 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to1.67 0.79 0.51 1.67 0.79 0.51 anionic surfactant (active to active)Zwitterionic (weight % active) E4 N/A 29.7 3.75 3.75 3.75 C1 Tegobetaine L7V 30 3.75 3.75 3.75 Anionic (weight % active) SM2S AlphastepPC-48 37 2.25 4.75 7.35 2.25 4.75 7.35 Organic acids Sodium SodiumBenzoate, 100 0.50 0.50 0.50 0.50 0.50 0.50 Benzoate NF, FCC Citric AcidCitric Acid solution 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to to to to topH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium Chloride,100 0 0 0 0 0 0 Chloride USP Water Purified water, USP 100 Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. to to to to to to 100% 100% 100% 100% 100% 100%

TABLE 15 Activity E40 E41 E42 C32 C33 C34 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to 11 1 1 1 1 anionic surfactant (active to active) Zwitterionic (weight %active) E4 N/A 29.7 3.75 3.75 3.75 C1 Tego betaine L7V 30 3.75 3.75 3.75Anionic (weight % active) SM2S Alphastep PC-48 37 4.75 4.75 4.75 4.754.75 4.75 Organic acids Sodium Sodium Benzoate, 100 0.50 0.50 0.50 0.500.50 0.50 Benzoate NF, FCC Citric Acid Citric Acid solution 20 Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. to to to to to to pH pH pH pH pH pH 4.5 4.5 4.5 4.54.5 4.5 Other Sodium Sodium Chloride, 100 0 0.75 1.25 0 0.75 1.25Chloride USP Water Purified water, USP 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.to to to to to to 100% 100% 100% 100% 100% 100%

TABLE 16 Example Composition Information Viscosity (cps) E37 3.75%w/w/zwitterionic surfactant 7216 C29 2.25% w/w/anionic surfactant (SM2S)<100 0% w/w sodium chloride E38 3.75% w/w/zwitterionic surfactant 5737C30 4.75% w/w/anionic surfactant (SM2S) <100 0% w/w sodium chloride E393.75% w/w/zwitterionic surfactant NA C31 7.35% w/w/anionic surfactant(SM2S) <100 0% w/w sodium chloride E40 3.75% w/w/zwitterionic surfactant5737 C32 4.75% w/w/anionic surfactant (SM2S) <100 0% w/w sodium chlorideE41 3.75% w/w/zwitterionic surfactant 2033 C33 4.75% w/w/anionicsurfactant (SM2S) <100 0.75% w/w sodium chloride E42 3.75%w/w/zwitterionic surfactant 1376 C34 4.75% w/w/anionic surfactant (SM2S)<100 1.25% w/w sodium chloride

Inventive Examples E43-E50 and Comparative Examples C35-C42 Preparationand Measurement of Certain Compositions of the Invention with andwithout PS-111 as an Anionic Surfactant and Comparative Compositions

Compositions E43-E50 and Comparative Compositions C35-C42 were made inaccord with the following procedure: Unless otherwise indicated, allmaterials were added in amounts such that the compositions containresulting weight percent amounts of active as indicated for eachcomposition in Tables 17 and 19. For example, 3.75% w/w active ofcocamidopropyl betaine (as given in table 17, C35) corresponds to 12.5%w/w Tego betaine L7V, which has an activity of 30% w/w; 3.75% w/w/30%w/w=12.5% w/w.

Compositions E43-E50 and Comparative Compositions C35-C42 were made asfollows: To an appropriately sized vessel equipped with a hotplate andoverhead mechanical stirrer, the required amount of DI water,zwitterionic surfactant, anionic surfactant, and sodium benzoate areadded and mixed at 200-350 rpm until the mixture is homogeneous; for E2at 50° C., for E4 and C1 at room temperature. Then, citric acid (20% w/wsolution in DI water) is added at room temperature to adjust to thedesired pH value 4.4-4.6. Then, Structure PS-111 and Sodium chloride areadded and mixed until the mixture is homogeneous. Water was added inq.s. to 100 wt %, and the batch is allowed to mix until uniform beforebeing discharged to an appropriate storage vessel. Tables 17 and 19 listsuch compositions.

The Zero Shear Viscosity and Max. Foam Volume were measured in accordwith the Zero Shear Viscosity Test and Formulation Foam Test,respectively, as described herein. The results are shown in Table 18 and20. As a result and surprisingly, applicants discovered thatzwitterionic ester ammonioalkanoate surfactants can not only buildviscosity in compositions containing AOS and/or SM2S as the anionicsurfactant, but that such compositions also exhibit better foamabilitycompared to compositions with zwitterionic alkylamidoamine betainesurfactants.

TABLE 17 Activity E43 E44 E45 E46 C35 C36 C37 C38 Material Trade Name(%) wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % Zwitterionic (weight% active) E2 N/A 88.6 3.75 3.75 3.75 3.75 C1 Tego betaine 30 3.75 3.753.75 3.75 L7V Anionic (weight % active) AOS Bioterge AS- 39 3.75 3.753.75 3.75 40 SM2S Alphastep 37 2.25 2.25 2.25 2.25 PC-48 SodiumStructure PS- 94 3 3 3 3 hydrolyzed 111 potato starch dodecenyl-succinate Organic acids Sodium Sodium 100 0.50 0.50 0.50 0.50 0.50 0.500.50 0.50 Benzoate Benzoate, NF, FCC Citric Acid Citric Acid 20 Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. solution to to to to to to to to pHpH pH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium100 0.6 0.6 0.2 0.2 0.6 0.6 0.2 0.2 Chloride Chloride, USP WaterPurified 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. water, USP to to toto to to to to 100% 100% 100% 100% 100% 100% 100% 100%

TABLE 18 Foam Viscosity Volume Example Composition Information (cps)(ml) E43 3.75% w/w/zwitterionic surfactant 435000 340 C35 3.75%w/w/anionic surfactant (AOS) 34 269 0% w/w Structure PS-111 0.6% w/wsodium chloride E44 3.75% w/w/zwitterionic surfactant 46000 360 C363.75% w/w/anionic surfactant (AOS) 75 280 3% w/w Structure PS-111 0.6%w/w sodium chloride E45 3.75% w/w/zwitterionic surfactant 32000 245 C372.25% w/w/anionic surfactant (SM2S) 4 154 0% w/w Structure PS-111 0.2%w/w sodium chloride E46 3.75% w/w/zwitterionic surfactant 2500 330 C382.25% w/w/anionic surfactant (SM2S) 30 280 3% w/w Structure PS-111 0.2%w/w sodium chloride

TABLE 19 Activity E47 E48 E49 E50 C39 C40 C41 C42 Material Trade Name(%) wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % Zwitterionic (weight% active) E4 N/A 29.7 3.75 3.75 3.75 3.75 C1 Tego betaine 30 3.75 3.753.75 3.75 L7V Anionic (weight % active) AOS Bioterge AS 39 5.75 5.755.75 5.75 40-CP SM2S Alphastep 37 3.74 3.74 3.74 3.74 PC-48 SodiumStructure 94 3 3 3 3 hydrolyzed PS-111 potato starch dodecenyl-succinate Organic acids Sodium Sodium 100 0.50 0.50 0.50 0.50 0.50 0.500.50 0.50 Benzoate Benzoate, NF, FCC Citric Acid Citric Acid 20 Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. solution to to to to to to to to pHpH pH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium100 1.45 1.45 0.2 0.2 1.45 1.45 0.2 0.2 Chloride Chloride, USP WaterPurified 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. water, USP to to toto to to to to 100% 100% 100% 100% 100% 100% 100% 100%

TABLE 20 Foam Viscosity Volume Example Composition Information (Cps)(ml) E47 3.75% w/w/zwitterionic surfactant 75000 435 C39 5.75%w/w/anionic surfactant (AOS) 175 307 0% w/w Structure PS-111 1.45% w/wsodium chloride E48 3.75% w/w/zwitterionic surfactant 43000 425 C405.75% w/w/anionic surfactant (AOS) 348 353 3% w/w Structure PS-111 1.45%w/w sodium chloride E49 3.75% w/w/zwitterionic surfactant 2300 330 C413.74% w/w/anionic surfactant (SM2S) 1 154 0% w/w Structure PS-111 0.2%w/w sodium chloride E50 3.75% w/w/zwitterionic surfactant 1300 365 C423.74% w/w/anionic surfactant (SM2S) 4 257 3% w/w Structure PS-111 0.2%w/w sodium chloride

Inventive Examples E51-E52 and Comparative Example C43 Preparation andMeasurement of Certain Compositions of the Invention with NonionicSurfactants and Conditioning Polymer and Comparative Compositions

Compositions E51-E52 and Comparative Composition C43 were made in accordwith the following procedure: Unless otherwise indicated, all materialswere added in amounts such that the compositions contain resultingweight percent amounts of active as indicated for each composition inTable 21. For example, 3.75% w/w active of cocamidopropyl betaine (asgiven in table 21, C43) corresponds to 12.5% w/w Tego betaine L7V, whichhas an activity of 30% w/w; 3.75% w/w/30% w/w=12.5% w/w. CompositionsE51-E52 and Comparative Composition C43 were made as follows: To anappropriately sized vessel equipped with a hotplate and overheadmechanical stirrer, 90% of the required amount of DI water, all PEG-80Sorbitan Laurate, and Polyquaternium-10 dispersed in glycerin were addedand the batch was heated to 80-85° C. under mixing. When temperaturereached 55° C., PEG-150 Distearate was added and mixed until the batchreached 80-85° C. and was uniform. The heat was turned off and RhodapexEST-65 (STDES) was added, mixed until uniform. Then, the zwitterionicsurfactant was added and the batch was mixed until the mixture washomogeneous. Versene 100 XL, sodium benzoate, and Euxyl PE 9010 wereadded and mixed until the mixture was homogeneous. When the batch hadcooled below 50° C., citric acid (20% w/w solution in DI water) wasadded to adjust to the desired pH value 5.2-5.4. Water was added in q.s.to 100 wt %, and the batch was allowed to mix until uniform before beingdischarged to an appropriate storage vessel. Table 21 lists suchcompositions.

The Zero Shear Viscosity and Max. Foam Volume were measured in accordwith the Zero Shear Viscosity Test and Formulation Foam Test,respectively, as described herein. The results are shown in Table 22. Asa result, applicants discovered that zwitterionic ester ammonioalkanoatesurfactants have the tendency to build higher viscosity in comparison tozwitterionic alkylamidoamine betaine surfactants in compositionscontaining anionic surfactant and several other formulation ingredients,like non-ionic surfactants (e.g. PEG80 sorbitan laurate), chelatingagent, glycerin, a cationic conditioning polymer (Polyquaternium-10) anddifferent preservatives. Such compositions also exhibit equivalent orbetter foamability in comparison to the equivalent compositionscontaining zwitterionic alkylamidoamine betaine surfactants.

TABLE 21 Activ- E51 E52 C43 Material Trade Name ity (%) wt. % wt. % wt.% E2 N/A 88.6 3.2 E4 N/A 29.7 3.2 C4 Tego betaine 38 3.2 F50 SodiumTrideceth Rhodapex 65 2.41 2.41 2.41 Sulfate EST-65 PEG-80 SorbitanAtlas G-4280 72 3.2 3.2 3.2 Laurate PEG-150 Exthox PEG- 100 1.1 1.1 1.1Distearate 6000 DS Special Polyquaternium- Ucare JR-400 100 0.14 0.140.14 10 Glycerin Emery 917 99.7 0.5 0.5 0.5 Tetrasodium Versene 100XL 380.2 0.2 0.2 EDTA Sodium Benzoate Sodium 100 0.30 0.30 0.30 Benzoate, NF,FCC Phenoxy ethanol Euxyl PE 100 0.7 0.7 0.7 and ethyl- 9010hexylglycerin Citric Acid Citric Acid 20 Q.S. to Q.S. to Q.S. tosolution pH 4.5 pH 4.5 pH 4.5 Water Purified 100 Q.S. to Q.S. to Q.S. towater, USP 100% 100% 100%

TABLE 22 Example Viscosity (cps) Foam Volume (ml)* E51 11200 217 E5210400 354 C43 2600 210 *Tested at 0.5 wt % in simulated hard water.

Inventive Examples E53-E60 and Comparative Examples C44-C47 Preparationand Measurement of Certain Compositions of the Invention with PS-111 andNonionic Surfactants and Comparative Compositions

Compositions E53-E60 and Comparative Compositions C44-C47 were made inaccord with the following procedure: Unless otherwise indicated, allmaterials were added in amounts such that the compositions containresulting weight percent amounts of active as indicated for eachcomposition in Tables 23 and 24. For example, 3.75% w/w active ofcocamidopropyl betaine (as given in table 23, C44) corresponds to 12.5%w/w Tego betaine L7V, which has an activity of 30% w/w; 3.75% w/w/30%w/w=12.5% w/w. Compositions E53-E60 and Comparative Compositions C44-C47were made as follows: To an appropriately sized vessel equipped with ahotplate and overhead mechanical stirrer, 90% of the required amount ofDI water, zwitterionic, anionic surfactants (Rhodapex ES-2K and,Structure PS-111), and the Polyaldo surfactant were added and the batchwas mixed at 200-350 rpm until the mixture was homogeneous. Citric acid(20% w/w solution in DI water) was added to adjust to the desired pHvalue 4.4-4.6. Sodium benzoate and sodium chloride were added. Water wasadded in q.s. to 100 wt %, and the batch is allowed to mix until uniformbefore being discharged to an appropriate storage vessel. Tables 23 and24 list such compositions.

The Zero Shear Viscosity and Max. Foam Volume were measured in accordwith the Zero Shear Viscosity Test and Formulation Foam Test,respectively, as described herein. The results are shown in Table 25. Asa result, applicants discovered that zwitterionic ester ammonioalkanoatesurfactants have the tendency to build higher viscosity in comparison tozwitterionic alkylamidoamine betaine surfactants in compositionscontaining anionic surfactants and several other formulationingredients, like polyglycerol ester surfactants. Such compositions alsoexhibit equivalent or better foamability in comparison to the equivalentcompositions containing zwitterionic alkylamidoamine betainesurfactants.

TABLE 23 Activity E53 E54 E55 E56 C44 C45 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to0.87 0.87 0.87 0.87 0.87 0.87 anionic surfactant (active to active)Zwitterionic (weight % active) E1 N/A 28.1 3.75 3.75 E4 N/A 29.7 3.753.75 C1 Tego betaine L7V 30 3.75 3.75 Anionic (weight % active) SodiumRhodapex ES-2K 26 3.3 3.3 3.3 3.3 3.3 3.3 laureth-2 Sulfate PS-111Structure PS-111 94 1 1 1 1 1 1 Nonionic (weight % active) Polyaldo10-1-L 100 1 1 1 Polyaldo 10-1-O 100 1 1 1 Organic acids Sodium SodiumBenzoate, 100 0.50 0.50 0.50 0.50 0.50 0.50 Benzoate NF, FCC Citric AcidCitric Acid solution 20 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to to to to topH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5 Other Sodium Sodium Chloride,100 0.47 0.47 0.47 0.47 0.47 0.47 Chloride USP Water Purified water, USP100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to to to to to 100% 100% 100% 100%100% 100%

TABLE 24 Activity E57 E58 E59 E60 C46 C47 Material Trade Name (%) wt. %wt. % wt. % wt. % wt. % wt. % Weight ratio zwitterionic/amphoteric to0.51 0.51 0.51 0.51 0.51 0.51 anionic surfactant (active to active)Zwitterionic (weight % active) E1 N/A 3.75 3.75 E4 N/A 29.7 3.75 3.75 C1Tego betaine L7V 30 3.75 3.75 Anionic (weight % active) Sodium RhodapexES-2K 26 6.3 6.3 6.3 6.3 6.3 6.3 laureth-2 Sulfate PS-111 1 1 1 1 1 1Nonionic (weight % active) Polyaldo 10-1-L 1 1 1 Polyaldo 10-1-O 1 1 1Organic acids Sodium Sodium Benzoate, 100 0.50 0.50 0.50 0.50 0.50 0.50Benzoate NF, FCC Citric Acid Citric Acid solution 20 Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. to to to to to to pH pH pH pH pH pH 4.5 4.5 4.5 4.5 4.5 4.5Other Sodium Sodium Chloride, 100 1.22 1.22 1.22 1.22 1.22 1.22 ChlorideUSP Water Purified water, USP 100 Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. to to toto to to 100% 100% 100% 100% 100% 100%

TABLE 25 Example Viscosity (Cps) Foam Volume (ml) E53 10400 280 E55 7000320 C44 457 279 E54 41000 270 E56 23000 300 C45 1685 280 E57 34000 320E59 26000 390 C46 25240 390 E58 73000 380 E60 57000 390 C47 16490 359

Inventive Example E61 and Comparative Example C48 Preparation andMeasurement of Certain Compositions of the Invention Equivalent toCommercial Formulations

Composition E61 and Comparative Composition C48 were made in accord withthe following procedure: All materials were added in amounts asindicated for each composition in Tables 26. For example, 16.4% w/w E4(as given in table 26, E61) had been added, which corresponds to anactivity of 4.87% w/w active of the3-((3-(lauroyloxy)butyl)dimethylammonio)-2-hydroxypropanesulfonate;16.4% w/w*29.7% w/w=4.87% w/w. Compositions E61 and ComparativeComposition C48 were made as follows: To an appropriately sized vesselequipped with a hotplate and overhead mechanical stirrer, 90% of therequired amount of DI water was added, stirred at 200-350 rpm and heatedto 35-40° C. The Carbopol ETD2020 was sifted slowly into the vortex. Themixture was stirred until the polymer was fully dispersed. The pH wasadjusted to 6.0-6.2 by adding 50% w/w NaOH in water. The StructurePS-111 was sifted slowly into the mix under stirring. The mixture wasstirred until homogenous. The Rhodapex ES-2K, the zwitterionicsurfactant and the sodium benzoate were added to the mixture. Themixture was stirred until homogeneous. The Natural Extract Scent wasadded and the mixture homogenized. The Jaguar C17 was dispersed intoglycerin in a separate vessel. This dispersion was added slowly into themixture under stirring. The Euperlan PK3000 AM was added to the mixtureunder stirring. The pH was adjusted to pH 4.5-4.9 using citric acid.Water was added in q.s. to 100 wt %, and the batch is allowed to mixuntil uniform before being discharged to an appropriate storage vessel.Table 26 lists the compositions.

The Zero Shear Viscosity and Max. Foam Volume were measured in accordwith the Zero Shear Viscosity Test and Formulation Foam Test,respectively, as described herein. The results are shown in Table 27. Asa result, applicants discovered that zwitterionic ester ammonioalkanoatesurfactants have the tendency to build higher viscosity in comparison tozwitterionic alkylamidoamine betaine surfactants in compositionscontaining anionic surfactants and several other formulationingredients, like cationic guar (conditioning polymer), hydrophobicallymodified acrylate crosspolymer (rheology polymer), glycol distearate(pearlizing agent) and fragrance. Such compositions also exhibitequivalent or better foamability in comparison to the equivalentcompositions containing zwitterionic alkylamidoamine betainesurfactants. Applicants note the comparative examples are normalized tothe same surfactant concentrations (% w/w active) as correspondingInventive Example (C48 corresponds to E61).

TABLE 26 E61 wt. % C48 wt. % Activ- of Materi- of Materi- Material TradeName ity (%) al as-is al as-is E4 N/A 29.7 16.4 C4 Tego betaine 38 12.4F50 Sodium laureth-2 Rhodapex 26 17.5 17.5 Sulfate ES-2K PS-111Structure 100 2.5 2.5 PS-111 Acrylates/C10-30 Carbopol 100 0.1 0.1 AlkylAcrylate ETD2020 Crosspolymer Guar Hydroxy- Jaguar C17 100 0.5 0.5propyltrimonium Chloride Glycerin Glycerin 99.7% 99.7 1 1 Min USP KosherGlycol Distearate Euperlan 2.5 2.5 (and) Laureth-4 PK3000 AM (and)Cocamidopropyl Betaine Dissolvine 100 0.63 0.63 GL-47-S FragranceNatural Extract 100 0.2 0.2 400-187 Part No. 06136 Sodium BenzoateSodium Benzoate, 100 0.50 0.50 NF, FCC Sodium Hydroxide 100 Q.S. to Q.S.to Pellets NF/FCC pH 4.5 pH 4.5 Grade Citric Acid Citric Acid 20 Q.S. toQ.S. to solution pH 4.5 pH 4.5 Water Purified 100 Q.S. to Q.S. to water,USP 100% 100%

TABLE 27 Example Viscosity (Cps) Foam Volume (ml) E61 139600 336 C4832110 323

Example E62 and Comparative Examples C49-C50 Preparation and Measurementof Certain Compositions of the Invention Containing No AnionicSurfactant and Comparative Compositions

Composition E62 and Comparative Compositions C49-C50 were made in accordwith the following procedure: All materials were added in amounts asindicated for each composition in Tables 28. For example, 7% w/w E4 (asgiven in table 28, E62) had been added, which corresponds to an activityof 2% w/w active of the3-((3-(lauroyloxy)butyl)dimethylammonio)-2-hydroxypropanesulfonate; 7%w/w*29.7% w/w=2% w/w. Compositions E62 and Comparative CompositionC49(50) were made as follows: To an appropriately sized vessel equippedwith a hotplate and overhead mechanical stirrer, 90% of the requiredamount of DI water was added, stirred at 200-350 rpm. The Carbopol 1382was sifted slowly into the vortex. The mixture was stirred until thepolymer was fully dispersed. Sodium benzoate was added to the mixtureand stirred until uniform. After adding glycerin, the batch was heatedto 65-70° C. The pH was adjusted to 6.0-6.5 by adding 50% w/w NaOH inwater. Plantaren 2000 N UP; Tegobetain L7V; Lamesoft PO 65; Polyaldo10-1-L had been added one by one under stirring mixed until uniform. Theheating was removed and the mixture was allowed to cool. At 55-60° C.Euxyl PE9010 was added. The pH was adjusted to 5.3-5.8. Water was addedin q.s. to 100 wt %, and the batch is allowed to mix until uniformbefore being discharged to an appropriate storage vessel. Compositionsprepared are listed in Table 28.

The Zero Shear Viscosity and Max. Foam Volume were measured in accordwith the Zero Shear Viscosity Test and Formulation Foam Test,respectively, as described herein. The results are shown in Table 29. Asa result, applicants discovered that zwitterionic ester ammonioalkanoatesurfactants have the tendency to build higher viscosity in comparison tozwitterionic alkylamidoamine hydroxy sultaine (Mirataine CBS) andbetaine surfactants in compositions containing anionic surfactants andseveral other formulation ingredients. Such compositions also exhibitequivalent or better foamability in comparison to the equivalentcompositions containing zwitterionic alkylamidoamine hydroxy sultaineand betaine surfactants. Applicants note the comparative examples arenormalized to the same surfactant concentrations (% w/w active) ascorresponding Inventive Examples (C49 and C50 correspond to E62).

TABLE 28 E62 C49 C50 wt. % wt. % wt. % of of of Activ- Material MaterialMaterial Material Trade Name ity (%) as-is as-is as-is E4 N/A 29.7 5.48C1 Tego betaine 30 7 L7V C3 Mirataine CBS 42 4.55 Coco-Glucoside;Lamesoft PO65 100 1 1 1 Glyceryl oleate Polyglyceryl-10 POLYALDO 100 1 11 Laurate 10-1-L Decyl Glucoside Plantaren 14 14 14 2000 N UPAcrylates/C10-30 Carbopol 1382 100 0.6 0.61 0.61 Alkyl Acrylate PolymerCrosspolymer (CBP1004) Glycerin 99.7% 100 1 1 1 Min USP KosherPhenoxyethanol; Euxyl PE 9010 100 0.9 0.9 0.9 Ethylhexyl- glycerinSodium Sodium 100 0.50 0.50 0.50 Benzoate Benzoate, NF, FCC Sodium 100Q.S. to Q.S. to Q.S. to Hydroxide pH 5.5 pH 5.5 pH 5.5 Pellets NF/FCCGrade Citric Acid Citric Acid 20 Q.S. to Q.S. to Q.S. to solution pH 5.5pH 5.5 pH 5.5 Water Purified water, 100 Q.S. to Q.S. to Q.S. to USP 100%100% 100%

TABLE 29 Example Viscosity (Cps) Foam Volume (ml) E62 2035 268 C49 2032209 C50 48350 222

Inventive Examples E63-E66 and Comparative Example C_(JBS) Preparationand Mildness Measurement of Certain Compositions of the Invention andComparative Compositions

Compositions E63-E66 had been made according to the process describedfor E-5. Table 30 lists these compositions.

The Zero Shear Viscosity, EpiDerm™ ET₅₀ and EpiOcular™ ET₅₀ weremeasured in accord with the Zero Shear Viscosity Test, EpiDerm™ Test andEpiOcular™ Test, respectively, as described herein. The results areshown in Table 31. As a result, applicants discovered that zwitterionicester ammonioalkanoate surfactants exhibit similar mildness incomparison to other zwitterionic surfactants like e.g. alkylamidoaminebetaine surfactants in compositions containing anionic surfactants.

TABLE 30 Activity Material Trade Name (%) E63 E64 E65 E66 E1 N/A 29.73.75 3.75 E3 N/A 3.75 3.75 Sodium Rhodapex ES-2K 26 3.3 6.3 6.3 10.3laureth-2 Sulfate Sodium Sodium Chloride, 100 0 0.75 0 0 Chloride USPSodium Sodium Benzoate, 100 0.50 0.50 0.50 0.50 Benzoate NF, FCC SodiumHydroxide 100 Q.S. Q.S. Q.S. Q.S. Pellets NF/FCC to pH to pH to pH to pHGrade 4.5 4.5 4.5 4.5 Citric Acid Citric Acid solution 20 Q.S. Q.S. Q.S.Q.S. to pH to pH to pH to pH 4.5 4.5 4.5 4.5 Water Purified water, USP100 Q.S. Q.S. Q.S. Q.S. to to to to 100% 100% 100% 100%

TABLE 31 REMOVE VISCOSITY Example EpiDerm ET₅₀ (h) EpiOcular ET₅₀ (h)E63 13 5.0 E64 11 1.9 E65 9.3 2.3 E66 7.5 1.5 C_(JBS) 14.1 1.88 JBS isJohnson's Baby Shampoo - a commercially available benchmark composition.

What is claimed is:
 1. A composition comprising a zwitterionic esterammonioalkanoate surfactant according to Formula 1,

and an ingredient selected from the group consisting of a surfactantother than said zwitterionic ester ammonioalkanoate surfactant,emulsifiers, conditioning agents, emollients, moisturizers, humectants,thickeners, lubricants, chelating agents, fillers, binding agents,anti-oxidants, preservatives, active ingredients, fragrances, dyes,buffering agents, exfoliates, pH adjusters, inorganic salts, solvents,viscosity controlling agents and opacifying agents, wherein saidzwitterionic ester ammonioalkanoate surfactant according to Formula 1comprises a zwitterionic ester ammonioalkanoate surfactant containing aheterocyclic group, and wherein said composition is substantially freeof alkylamidoamine and aminoalkylamine.
 2. The composition of claim 1wherein said composition is free of alkylamidoamine and aminoalkylamine.3. The composition of claim 1 wherein said surfactant other than saidzwitterionic ester ammonioalkanoate surfactant according to Formula 1 isselected from the group consisting of anionic surfactant, cationicsurfactant, non-ionic surfactant and zwitterionic surfactant.
 4. Thecomposition of claim 1 wherein said composition is substantially free ofan anionic surfactant.
 5. The composition of claim 1 wherein saidcomposition is substantially free of a sulfated anionic surfactant. 6.The composition of claim 1 wherein said zwitterionic esterammonioalkanoate surfactant according to Formula 1 comprises azwitterionic ester ammonioalkanoate sulfonate surfactant.
 7. Thecomposition of claim 1 comprising from about 0.1% to about 30% of saidzwitterionic ester ammonioalkanoate surfactant according to Formula 1.8. The composition of claim 1 comprising from about 1% to about 10% ofsaid zwitterionic ester ammonioalkanoate surfactant according toFormula
 1. 9. The composition of claim 3 wherein said zwitterionic esterammonioalkanoate surfactant according to Formula 1 and said surfactantother than said zwitterionic ester ammonioalkanoate surfactant accordingto Formula 1 are present at a weight ratio of from about 0.003 to about300.
 10. The composition of claim 3 wherein said zwitterionic esterammonioalkanoate surfactant according to Formula 1 and said surfactantother than said zwitterionic ester ammonioalkanoate surfactant accordingto Formula 1 are present at a weight ratio of from about 0.1 to about10.
 11. The composition of claim 1 having a pH of from about 3 to about9.
 12. The composition of claim 1 comprising from about 0.05 to about 6weight percent of said inorganic salt.
 13. The composition of claim 1wherein said composition is substantially free of a zwitterionicsurfactant comprising an amide moiety.
 14. The composition of claim 1wherein said composition is free of a zwitterionic surfactant comprisingan amide moiety.